Primary cells



Feb. 17, 1959 G. s. LozlER ET AL.

PRIMARY CELLS Filed June 13. 1956 United States Pte'nt 2,874,079 PRIMARY CELIS i Gerald S. Lozier, Princeton, Richard Glicksman, Highland Park, audClareuce K. Morehouse, Princeton,

N. J., assignors to Radio 'Corporation of America, a

corporation of Delaware v Application-June 13, 1956, Serial No. 591,094 '13 'Claims. (Cl. 1364-137) This invention relates to primary cells, and particularly; butnot necessarily exclusively, to improved primary cells including arr'aluminum anode and a cathode comprising a positive halogen organic compound.

. Primary. cells are .electrochemical devices from which stored chemical energy is converted directly into electrical energyby an electrochemical process. Generally, the term'primary cells refers to a class of cells that do not have eiciently reversible chemical reactions. Once the chemical energy is converted to electrical energy, the cells A of Standards, Washington, D. C.).

which 'comprises 70% are discarded. Primary cells that are manufactured to include a non-spillable electrolyte are referred to as dry cells. Primary cells that are assembled without one of the essential components, such as the electrolyte, but are adapted to supply electrical energy when the componelrli; is added just prior to use, are referred to as reserve ce A primary cell which is to be used as a portable power supply should have the following characteristics: a high watt-hour and a high ampere-hour capacity per unit of volume or weight; a high, fiat operating voltage over a wide range of current drains; a long life; and a low cost.

One problem in present day primary cells is that they include materials which come into short supply in times of emergency because they become critical to the interests of the United States as a whole. These materials may become critical because they are supplied from foreign sources or because domestic ore sources are limited in size and mining capacity, or for some other economic reason.

Accordingly, an object of this invention is to provide primary cells which are comparatively inexpensive to manufacture, have a high watt-hour and a high amperehour capacity per unit of volume or weight, and a relatively high, flat operating voltage level over a wide range of current drains. l

A further object is to provide an improved electrochemical system which may be employed in primary cells.

Another object is to provide improved primary cells including materials which are non-strategic, can be readily available in large quantities in the United States, and are comparatively inexpensive.

In general, the foregoing objects are accomplished `in improved primary cells of the invention which include an anode selected from the group consisting of aluminum and aluminum-base alloys and a cathode including an organic oxidizing substance 'in which the oxidizing properties are due at least in part to positive halogens chemically combined in said substance. The invention includes reserve ce1ls,. including the above-described .combination and adapted to be used to supply electrical energy upon the addition of an electrolyte or water.

The invention is described in greater detail by reference to the drawings wherein:

Figure 1 is a sectional, elevational view of a typical dry cell of the invention,

Figure 2 is a family of curves showing the change in cell voltage with respect to discharge time of a D size .dry cell of the invention compared with comparable dry 2,874,079 .Patented Een -17. 19.5.9.

2 cells from other electrochemical systems when discharged continuously through a 4 ohm resistance, `and Figure 3 is a family `of curves illustrating the discharge characteristics of a reserve cell of the invention when discharged continuously at 0.100 ampere constant current.

Example 1.-Referring to Figure l, a cell according to the invention may be prepared as'follows.` A metallic anode 12 is provided in the form of a cup :of the standard D size (American Standards'Assocation, Bureau The anode 12 is a duplex prodct"having an outer layer. comprising .an aluminum, 3% magnesium,.1% zincand 0.5% manga;l nesegfand an internal layer 'fof super-purity aluminumbyA weightof the' duplex product: This duplex alloy composition'is 'sometimes designated' Al-M-3-73. The anode 12 is lined with a'se'parator 14 comprising an absorbentkraft paper.- The separator14 keeps the anode 12 and a cathode 16 apart while provid# Y ing therebetween a low Vresistan'ce'path to the ow vof ions during the electrochemical process. Y

A mix including the cathode material and electrolyte,@ hereinafter referred to as the cathode mix is prepared of the following formulation: l -A I grams N, N dichloro-p-toluenesulfonamide 40 grams acetylene black v ml. aqueous solution .containing 480 'grams AlCl3-6H2O per liter of water y Approximately 45 grams of the cathode mix is formed to a cylindrical slug and inserted into the paperlined anode 12 to forma cathode 16. A carbon rod 18-is in-1 serted Vinto the cathode mix 16 to provideelectrical connection thereto. The anode 12 is sealed with an insulating washer 20 mounted on the carbon rod and a layer 22 of hard wax on the washer 20. A metal contact cap 24 of brass is placed on rod 1,8. An air space 26 is provided between the washer 20 and the cathode 16.

The anode and cathode may now be connected through an external load whereby the celll commences to be dis-k charged by electrochemical action. The cell reactions are believed to occur as follows: f

C. OVERALL CELL REACTION satana zarten).

CHS CH3 Figure 2 shows characteristic initial discharge curvesfor D size dry cells discharged continuously through a. 4 ohm load resistance (simulating the current drain re-y quirements in a ilashlight). .Curve -31 shows a'characteristic discharge curve alloy :with the; composition 95.5%."

for a cell. prepared vaccording .to.

225 grams manganese dioxide 25 grams acetylene black 20 grams `(.lSlIrIihCrOiA grams CrCla'ioHQ' 61 .mluaier" dry cell of ExampleV 1 operates at a .considerablyhighervoltage than the comparable zinc/manganese .doxide and aluminumlmanganese dioxide dry cells. It should also be noted that the cell ofv Example l has a desirable high atvoltage curve.

In addition to its favorable performance, the cell of Example l1 has the great advantage that it employs nonstrategic, plentiful materials which are relatively easy to manufacture in the United States, and when manufacf tured in large quantities, should be relatively inexpensive. Aluminum may be obtained from clay and the N.N dichlorofnrtoluencsulfonamide may be produced synthetically.

The primary cells Qf the .invention comprise generally the following parts :v A i (l)IV An anode selected from the group of materials consisting of aluminum and aluminum-base alloys,

(2) An electrolyte which may include (a)` a soluble substance for increasing theY electrical-conductivity there of and (b) a material for inhibiting the corrosion of the anode,

(3) A cathode including a depolarizer consisting of an organic oxidizing substance in which the oxidizing properties thereof are due at least in part to chemically combined positive halogens. The cathode may include also an inorganic depolarizer, other organic depolarizer and/or an inorganic material for increasing the conductivity o f the cathode.

v[he qnode.f-The anode for the primary cells of the invention may be aluminum or aluminum-base alloys. The term aluminum anode includes both aluminum and aluminum-base alloy anodes. An aluminum-base alloy is one wherein the predominant ingredient is aluminum. Thus, any alloy having more than 50% aluminum is satisfactory. It is preferred however, to have as high a proportion as possible. Other ingredients are added to aluminum to improve the properties of the anode for fabrication purposes, to impartfa greater degree of corrosion resistance or for other reasons. Table I sets forth examples of some suitable aluminum anode materials.Y

`Table I Alloy and Temper Composition Colrimercially pure aluminum.

taf-aluminum onfone or both sides. A duplex product madeof a 24S-T core and coatings otalumtnum on one or both sides.

geraet@ cell, may be the lining of the container, or may be a separate structure inserted in the container. The aluminum anode may be in any geometrical configuration desired. In Example l, a paper separator lined the aluminum anode cup 12. It is necessary to space the cathode from the anode. To accomplish this, it is preferred to insert a separator between the anode and cathode regardless of conliguration, although other methods may be used. The separator may be any porous material; kraft paper, porous ceramics, or other inorganic or organic structures.

The electrolyte.-The electrolyte may be water containing a soluble salt such as sea water or water to which one or more soluble salts 4have been deliberately added. Bromids and VVchica-hides of alkali met-als," alkaline earth metals, aluminum, chromic, manganous, and ferric cations are suitable soluble salts in the electrolyte. The` electrolyte may be prepared by dissolving the hydrated salt in water in a concentration between about 30 grams per liter and that which produces a saturated solution at ordinary temperatures. The concentration does not apf pear to be critical although forrbcst resultsccrtain conf centrations areY preferred depending upon the particular salt or combination of salts that are used. For example, 'preferred concentrations of the hydrated aluminum metal chloride are from about :69() grams, prefer-V ably 480 grains of hydrated salt per liter of Water. While a Single Salt may be used as tlieelectrclyte. combinations ofV salts, particularly combinations of alumi. num chloride and chromic chloride are desirable. Examples oif soluble salts that may be added to the electrolyte are zinc c hlorida'manganous chloride, magnesium bromide. magnesium chloride, aluminum chloride, ammflium Chloride. chiami? chloride( alkali metal chlorides., potassium Chloride and calcium chloride it is also desirable to include in the electrolyte one or more alkali metal.. alkaline earth metal (including aluminum) or ammonium salts of chromic acid in corrosionlinhibiting amounts. The chromic acid salts may be used in proportions'between O-.Ol gram per liter of solution to concentrations producing saturation in the presence of the electrolyte salt contained therein. lt is preferred to use a proportion equal to that of the electrolyte salt for dry cells. Examples of corrosion-inhibiting salt'sare sodium chromate, aluminum chromate, Potassium diliramaie lithium dichrmate, magnesium chromate, calcium chromate, ammonium chromate, and ammonium d ichromate.

For certain applications, principally where a long shelf life is desired, it is desirable to omit one of the compounds ofr the primary cell, until the need for electrical energy.` hasariseu. The primary cells of the invention are particularly adaptable to be prepared as reserve cells, In, reserve cells, materials corrosive to the anc-de such as aqueousl solutions of, aluminum chloride, chromic acidl and phosphoric acid, may `be-fusedto, enhance thef voltage of the cell.

The cathode-The cathole includes' an organic oxidizing substance in which the oxidizing properties are 0 where X designates any one of the halogen group:

chlorine, brornine and iodine. Thus a test for a positive halogen comprises reacting the material question with an aqueousy solution of` an iodine c,ornpoxindv whichA is oxidized by: the. hypohalous acid liberated, by the reaction ofi the' substance with water, liberating iodine. For

These substances are also referred to as posi-v Some of .thepositive halogen organic compounds are relatively insoluble in conventional electrolytes and are particularly suitable as cathode ymaterials in dry cells. Some of the insoluble positive halogen organic comv pounds are also liquids which are immiscible with the electrolyte and can be adsorbed by a material such as acetylene black or graphite. Some of the positive A. Amines of the general formula RNHX, RNXZ, RRNX where R is an alkyl radical. A typical example of this class is: N,N dichloromethylamine B. Amides 1. Carboxylic Acid Amide's Aliphatic monocarboxylic acid amides:

Nch1oroacetamide N-bromoacetamide l Alphatic dicarboxylic acid amides:

N,N dibromosuccinamide N,N"dibromooxamide l N,N' dibromoadipamide Aromatic monocarboxylic acid amide N-brornobenzamide Aromatic dicarboxyl acid amides: N,N dibromoterephthalamide 2. Sulfonic Acid Amides of the RSOONHX and-RSOONXZ Sodium salt of N-chlorobenzenesulfonamide. Sodium saltof Nchloro-p-toluenesulfon-amide N,N-dichloro-p-.toluene sulfonamide and N,N

dibromo-p-toluenesulfonamide N,N-dichloro-benzene sulfonamide and N,N dibromo-p-benzenesulfonamide N,N-dichloro-p-carboxylic acid-benzene l fonamide Y 3. Derivates of Carbonic Acid Amides N,N dichloro. or dibromobuiret C. Imides Derived from Dibasic Acids N-chlorosuccinimide N-bromosuccinimide N-bromophthalimide Ethyl-N-bromophthalimide D. Quinone Imides N,2,6 trichloro-p-quinoneimine N-chlorofp-quinoneimine E. Cyclic Ureides 'j' N-monochloro and monobromo dimethylhydantoin N,N dichloro and dibromo dimethylhydantoin N,N dibromobarbituric' acid N,N' dichloro and dbrornodiphenylhydantoin F. Amidines of Carbonic Acid v Trichloromelamine and tribromomelamine Hexachlormelamine Penta and tetra chloromelamines-these are mix- ,tures of trichloro and hexachlormelamines N,N' dichloroazodicarbonamidine Trichloroisocyanuric acid N-chloroacetoguanamine N-chloropropiguanamine Nchlorodicyandiamide y Y G. Pyrroldones" Y o l Polyvinyl pyrrolidone with 40% iodine' Formula sul- of active surface 011l the cathode.

Any positive halogen organic compound may be used as cathodes of the primary cells ofthe invention. The primary cells` of the invention all utilize the electron change'obtained in converting a positive halogen vion to a negative halogen ion. This is shown schematically by the following equation where X is a halogen:

Inv addition, such compounds may have other radicals in their structure'which alterl their physical and chemical properties to` affect the stability and solubility in the electrolyte. It is also recognized that by changing the structure of the positive halogen organic compounds, the theoretical capacity, shelf. life and the rate at which electrical energy can be withdrawn from the cell can be altered. The selection of the particular compound and vits structure will depend on the application for which the'particular vprimary cell is intended. The utility of the positive halogen organic compound may be further enhanced by the presence of oxidizing groups such as nitro, azo, etc. vgroups which will increase the theoretical capacity. The cathodes of the primary cells of the invention may also comprise a mixture of one yor more positive halogen organic compounds, ora mixture with one or more other organic oxidizing compounds, such as quinone, or certain organic azo compounds, or with inorganic cathode materials such as manganese dioxide or the like.' y v For many situations, it is desirable Vto increase the electrical conductivity of the cathode. One may add varying proportions of non-reactive conductive materials to obtain the desired electrical conductivity. Carbon is a preferred material. for this purpose because of its low cost and easy availability. Any of the various forms of carbon, such as graphite, or acetylene black may be used. The conducting'material may comprise up to 80% by weight of the cathode mix. l l

The cathodes'of the invention may be fabricated bya number of methods and in various shapes. Example l describes preparing a mixture of powders with electrolyte and then pressing a quantity of the mixture to the desired shape and density. Another cathode mix may include a binder such as polyvinyl alcohol, carboxymethylcellulose, methylcellulose, 4a vinyl resin, bentonite or silica gel. Such mix may be pressed as described above, or cast in' a mold to fabricate the cathode. -The binder adds strength and rigidity to the cathode especially where odd shapes are used. A cathode mix containing a binder may be coated on a suitable support such as a carbon rod or black and used in layer form. Besides simple coatings, lms containing the cathode mix may also Abe prepared by the addition of a film-forming material to the cathode mix and using techniques well-known in the plastics art. One technique' is to coat paper separator sheets with aluminum powder in a binder on one surface and the cathode mix in a binder on the other surface. The coated sheets may then be stacked and stamped to produce batteries of the desired voltage and geometry.

Many of the positive halogen organic compounds used in the cathodes of the invention melt at relatively low temperatures without decomposition. N,N' dichlorodimethylhydautoin, for example, melts at C. The cathode mix may be prepared by mixing the dry powders, fusing and then pulverizng the fused product. The pulverized product may then be fabricated into cathodes by one of the methods described above. By another method and upon fusion, the cathode mix may be cast directly Vto the desired shape either in a mold or directly in the place where it is to be used.

In some cases, it is desirable to increase the amount One method for increasing the activeV surface is to add a proportion of a soluble material, such as sodium chloride, to the cathode mix before fabrication. Upon fabrication, the soluble n n-rante materiel ie. .dissolved .ont of .the cathode :leaving .e .eenie- Wllet Perrine stiltetnre with e .greatly increased Prorettion of active surface. Y

. The Presente of etmeepherie .oxygen .enhances the Capacity ef the .eethesie oteells of various kinde- For example Capacity increases een Vbe realized yin the Celle of Figure 1 by providing a small vent (e. g., 0.05 inch in diameter) in the wax layer ,22 zby preparing a tab on the washer which tab 20 extends up through the wax seal 22. The maximum veffect is ordinarily Yobtained when the current .drain .is .relatively light.

It is noteworthy that the .materials `used Ato fabricate the c ells .of the invention may `all be producedin the United -States .by .processes well known .in the chemical arts. The positive ha-logen organic compounds may Lbe produced `synthetically .and many such substances such as N,N .dichlorodimethylhydantoin, are commercially available 4atthe .present time. Graphite fand acetylene black .are also available from sources .within the United States.

Example j2..- A .reserve cell mayzbeprepared as follows. Prepare .a eathodemix of the `following ingredients:

2O lgrams' N gN `diciilorodimethylhydanton 10 grams graphite Heat this .mixture until .it is .molten `(about 140 CJ. pour 'themolten mass Linto a Ipaper lined can (I. D. 0.3.95fl1eight .1'.8.24")., ;1n.Se.r.t n carbon rod, and then allow the mass to solidify. Upon cooling remove the solid .mass yfrom the can, .Wrap .with .a piece of .absorbent nonfwovenffehrie material. lhen nl aeeapiece 0.5.0012 thick-aluminum sheet (Super purity) aroundthezassembly and bind witha wire. The .assemblyhas the following approximate-size: height.. 1,252 diameter, .0,50";-.vo1ume, 0-.25 ou. in.; .and .the followine `Weights: carbon rod, 1.3 a; .Cathode material, 0.7 e.; .cell (dry) .4,0 gasell (wet) 5.04%. ,This .eellnravbe .Stored .for n period of time and when desired for use, Lis immersedpinlan aqueous solution .containing 4.80 grains .of .A1.C13'6H2O .per vliter of Water.

Example 3-A vliet reserve .cell which .operates rat very high Adischarge rates may be prepared bydrst mixing ,the Lfollowing ingredients .to Prepare raathode mix:

100 grams `l\l,N dichlorodimethylhydantoin 50 rgrams acetylene black 26 ml. solution'containing 3% animal glue dissolved in acetone Pastea quantity of the cathode mixto -a graphite plate about 2.75 x 1.1875 .x 0.50" thick. rihe cathode is wrapped with a piece -ofsalt-free kraft paper and then wrapped .with a sheet. The assembly was then immersed in an aqueous solution containing A80 grams AlCl3'6H2O per liter of water. YFigure 3 shows char acteristic discharge curves of .this cell compared with similar size zinc/N,N' dichlorodimethylhydantoin cells under a constant current drain of 0.100 ampere.

Example l1.-Another dry cell of the invention may be prepared according to Example 1 except that Ythe cathode mix comprises the following formulation:

8:0 grams trichloromelamine 40 .grarns acetylene black fsreine .ammonium ehrotnete 100 ml. aqueous vsolution ycontaining 480 grams AlCl-.l-IZO per liter of'water Example 5.-Another dry cell of the invention may be prepared 'according A*to 4Example l1 except that the cathode mix comprises the -following formulation:

8.0,sran1s .hexaehloronielanine 4 0 grams acetylene Ablack 3,0;grams ammonium chromatic l 1.00 ..1.n1- .aqueous solution .containing A80- :seams .'6Ha0 L'Il' liter Qf Wal-'e1' Exemple ie-.Another Qty eetl ef .the .invention nav be'nreper'eti .eeeer'ns .te .Exemple l exeept 1that tile cathode mix comprises the following formulation: graine NN Veliehleteeznflieetbeneniitiine 40 grams acetylene black ml. vaqueous solution containing 400 grams MnGl2-4H2`O and 5 grams vNazCrQf, per liter of`water AlCls-'HzQ per liter of water .Exemple S-:fanether .dry .eell `of the invent-.ien .tney be preparen eeeettlins to .Exemple .1 exeent ,that the cathode mix comprises the following formulation:

240 grams hexachloromelamine 240 grams manganese dioxide grams acetylene black 80 grams sodium dichromate 670 ml. aqueous solution containing 480 grams AlCl3-6H2O per liter of water.

There have bcn described improved primary cells which are inexpensive to manufacture .and exhibit a high watt-hour and ampere-hour capacity. per unit or value of watt and a high at operating voltage level over a wire range of current drains. The cells of the invention use materials which may be produced within the United 4States in large quantities by .techniques well 1rrnown in the chemical art.

What is claimed is:

1. In a primary cell utilizing the yelectron change obtained inconverting a positive halogen ion to a negative halogen ion, an anode selected from the group consisting `of aluminum and aluminum base alloys in cornbination with a cathode including a depolarizer consisting of an organic oxidizing compound in which the oxidizing properties of said substance are due at least in part to positive halogens chemically combined in said compound, said compound being selected from the group consisting of `amines of the general formula RNHX, RNX3, RQNX where R is an .alkyl radical and X is a halogen atom, imides derived from rdiba'sic acids, cyclic ureides, carboxylic acid amides, `sulfonic acid amidcs, derivatives of carbonic acid amides, and of carbonic acid. l

2. A primary cell according vto claim 1 wherein said anode comprises an aluminum base alloy.

3. A primary cell according to claim l wherein said cathode comprises a mixture of differentorganic oxidizing compounds in which the oxidizing properties of at least one of said compounds are due at lleast in part to positive halogens chemically combined inslaidsubstances.

4. A .primary cell according to claim v1 wherein said cathode includes aninorganic depolarizer. i

S. A primary cell according to claim 1 wherein said cathode includes an inorganic material for increasing the electrical conductivity of said cathode.

6- A Printen .eelt .utilizing .the .eleetton .etrange btained in converting a positive halogen ion At'oanegativehelesenien .eentntieins .en aluminum anode, en le1eettelyte, ende .-eethetle inelttdins e tlenoleria'er `Consisting of an organic oxiding compouridfin x'which :the oxidizing properties are due at least `in part to positive :halogens chemically combined in said compound, w.said@compound being selected from the group consisting .of .amines of the general formula RNHXQRNXZ, 'lQNXwhe'rQR is an alkyl radical and X is a halogeny atomhigridesderlved from dibasie vragende,` cyclic ureides, oafbol acid amides, sulfonic 'acid amides, derivatives of carbonic acid amides, and amidines of carbonic acid.

7. A primary cell according to claim 6 wherein said electrolyte is an aqueous solution having dissolved therein a compound selected from the group consisting of aluminum chloride, manganese chloride, chromium chloride, ammonium chloride, zinc chloride, alkali metal chlorides and alkaline earth metal chlorides.

8. A primary cell according to claim 6 wherein said electrolyte is an aqueous solution having dissolved therein a chromic acid salt of an anion selected from the group consisting of alkali bases, alkaline earth metal bases and ammonium bases.

9. A primary cell utilizing the electron change obtained in converting a positive halogen ion to a negative halogen ion comprising an aluminum-base alloy anode, an aqueous electrolyte having dissolved therein aluminum chloride and a chromate inhibitor, and a cathode comprising carbon and an organic oxidizing compound in which the oxidizing properties areA due at least in part to positive halogens chemically combined in said compound, said compound being selected from the group consisting of amines of the general formula RNHX, RNXZ, RSNX where R is an alkyl radical and 1i)l X is a halogen atom, imides derived from dibasic acids, cyclic urcides, carboxylic acid amides, sulfonic acid amides, derivatives of carbonic acid amides, and amidines of carbonic acid.

10. A primary cell including an aluminum anode, an aqueous electrolyte and a cathode including N,N' dichlorodimethylhydantoin.

l1. A primary cell including an aluminum anode, an aqueous electrolyte and a cathode including N,N dichloro-p-toluenesulfonamide.

12. A primary cell including an aluminum anode, an aqueous electrolyte and a cathode including hexachloromelamine.

13. A primary cell including an aluminum anode, an aqueous electrolyte and a cathode including N,N dichloroazodicarbonamidine.

References Cited in the le of this patent UNITED STATES PATENTS 2,306,927 Arsem Dec. 29, 1942 2,343,194 Lawson Feb. 29, 1944 2,554,447 Sargent May 22, 1951 2,612,533 Blake Sept. 30, 1952 

1. IN A PRIMARY CELL UTILIZING THE ELECTRON CHANGE OBTAINED IN CONVERTING A POSITIVE HALOGEN ION TO A NEGATIVE HALOGEN ION, AN ANODE SELECTED FROM THE GROUP CONSISTING OF ALUMINUM AND ALUMINUM BASE ALLOYS IN COMBINATION WITH A CATHODE INCLUDING A DEPOLARIZER CONSISTING OF AN ORGANIC OXIDIZING COMPOUND IN WHICH THE ODIDIZING PROPERTIES OF SAID SUBSTANCE ARE DUE AT LEAST IN PART TO POSITIVE HALOGENS CHEMICALLY COMBINED IN SAID COMPOUND, SAID COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF AMINES OF THE GENERAL FORMULA RNHX, RNX2, R2NX WHERE R IS AN ALKYL RADICAL AND X IS A HALOGEN ATOM, IMIDES DERIVED FROM DIBASIC ACIDS, CYCLIC UREIDES, CARBOXYLIC ACID AMIDES, SULFONIC ACID AMIDES, DERIVATIVES OF CARBONIC ACID AMIDES, AND AMIDINES OF CARBONIC ACID. 